Detergent particles

ABSTRACT

The present invention relates to a method for making a laundry detergent particle comprising from 10 to 60 wt % (anhydrous basis) zeolite, from 12 to 75 wt % polycarboxylate polymer, and optional additional ingredients to 100% by weight, said method comprising preparing an aqueous slurry comprising zeolite, and polycarboxylate polymer and optional additional ingredients and spray drying the slurry. The weight ratio of zeolite (anhydrous basis) to polycarboxylate polymer in the slurry is from 4:1 to 1:2. The particles have been found to reduce caking of detergent product whilst providing improved cleaning compared with the addition of the polycarboxylate polymer as a separate granule. The invention also includes detergent compositions comprising such particles. The particles may be incorporated into a finished detergent composition as part of an agglomerate or extrudate.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority under 35 U.S.C. § 119(e) to EuropeanPatent Office Serial No. 03257082.2 filed Nov. 10, 2003.

TECHNICAL FIELD

The present invention relates to the field of laundry detergentcompositions and in particular to methods for making particles whichcomprise polymer and which are suitable for use in laundry detergentcompositions.

BACKGROUND OF THE INVENTION AND PRIOR ART

It is often desirable to incorporate polycarboxylate polymers intodetergent compositions as part of an effective builder system. They areavailable from suppliers as powder, in solution or in granular form.EP-A-421664 states that these types of polymers are generally added todetergent formulations either in the form of a dried powder that isformed by spray-drying a solution, dispersion, slurry or emulsion ofpolymer in a liquid (“wet polymer”), or directly as wet polymer to adetergent formulation in slurry form before drying. It is then statedthat in both cases the product has a number of undesirablecharacteristics: the powder formed by spray drying wet polymer is saidto be hygroscopic and therefore tends to become sticky upon storage orin the final formulation. EP-A-421664 solves the problem by providing anagglomerate made by agglomerating a dry polymer and an inorganiccomponent.

It is well known to incorporate these polymers into spray drieddetergent base granules. They are usually incorporated at low levels.DE-A-3316513 describes use of wet polymer to prepare a zeolite particle.The problem addressed is that of effectively dispersing zeolite inaqueous wash liquor in view of the water insoluble, finely particulatenature of zeolite. The particles disclosed contain 70 to 95 wt % zeoliteand 5 to 30 wt % polycarboxylic acid polymer. Polycarboxylate polymer isalso incorporated into spray-dried granules in EP-A-640 684 for makingphosphate-free automatic dishwashing compositions; WO92/13937 for makinga granular additive for pre-treating hard water or as an additive for acleaning composition with polymer at very high levels; EP-A-270 240 formaking low particle porosity spray-dried powders; and in EP-A-137 669for preparing detergent compositions that are phosphate-free butcomprise a bleach system having good bleach stability and fabric damagecharacteristics.

Trade literature from suppliers of these polycarboxylate polymers andpatent publications such as EP-A-658189 and EP-A-759463 teach that thesuppliers' granules consisting of these polymers (generally containingat least 90 wt % polymer) give the best building benefits, morespecifically anti-incrustation benefits.

However, the present inventors have found that polycarboxylate polymersincorporated into detergent formulations in the form of such polymergranules still result in caking of the detergent compositions. Inaddition, agglomeration of the dry powder polymer is expensive. It istherefore an object of the present invention to provide apolycarboxylate polymer in particulate form for addition to detergentcompositions in a cost-effective manner whilst overcoming the cakingproblems associated with these materials and without losing theiranti-incrustation benefits.

Definition of the Invention

In accordance with the present invention there is provided a method formaking a laundry detergent particle comprising from 10 to 60 wt %(anhydrous basis) zeolite, from 12 to 75 wt % polycarboxylate polymer,and optional additional ingredients to 100% by weight, said methodcomprising preparing an aqueous slurry comprising zeolite, andpolycarboxylate polymer and optional additional ingredients and spraydrying the slurry, characterised in that the weight ratio of zeolite(anhydrous basis) to polycarboxylate polymer in the slurry is from 4:1to 1:2.

In a preferred embodiment, the level of polycarboxylate polymer in theparticles produced is from 15 to 50 wt % and of zeolite (anhydrousbasis) is 10 to 50 wt %, or 29 to 50 wt %. A preferred additionalingredient comprises sodium carbonate.

In a further embodiment of the invention, detergent compositionscomprising particles made by this process are defined. The inventorshave found that detergent compositions comprising the particles madeaccording to this invention also provide improved cleaning under coldwater conditions when compared with the same compositions in which thepolymeric polycarboxylate is added as a separate granule. This issurprising in view of the suppliers trade literature and teachings suchas EP-A-658189 and EP-A-759463 which teach the use of granules of thesepolymeric materials in contrast to incorporating them via spray-dryingprocesses.

DETAILED DESCRIPTION OF THE INVENTION

The polycarboxylate polymers include homopolymers or copolymers.Suitable polymers include homopolymers or copolymers of dicarboxylicacids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid,citraconic acid and the derivatives of such acids including anhydridesof dicarboxylic acids, such as maleic anhydride; monocarboxylic acidssuch as acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acidand acryloxypropionic acid.

Polymers can be in acid or neutralized or partially neutralized formwith Na, K, or other counterions. Preferred polycarboxylate polymers arehomopolymers of acrylic acid and copolymers of acrylic and maleic acids.Especially preferred are the acrylic/maleic copolymers available fromBASF as Sokalan (tradename) CP5 and CP7 (salt form) and CP45 (acidform).

The average molar mass Mw of the polymers is typically from 500 to5,000,000. Preferably the molecular weight will be above 10 000, morepreferably above 20 000. The molecular weight may be below 1 000 000,but is usually below 500 000 or even 100 000.

Preferably the polymer will have a Brookfield viscosity (measured on aBrookfield LVT with a 20% solution of active substance in distilledwater at 23° C., spindle 1 at 60 rpm) of from 25 to 60, preferably 30 to50.

The amount of polymeric polycarboxylate in the particles produced by thepresent invention is from 12 to 75% by weight, or even from 15 to 50% byweight and the quantities incorporated into the slurry for spray dryingis selected accordingly. The quantities of polymer defined in thispatent application are based on the equivalent fully neutralised sodiumsalt form of the polymer; for acid forms of polymer or other salt forms,the amounts used should be adjusted accordingly to be within the rangesdefined.

The zeolite (alkali metal aluminosilicate) is present in an amount offrom 10 to 54 wt % (based on anhydrous material). Preferably there willbe at least 12 wt % and more preferably at least 15 wt % or at least 20wt % zeolite or even at least 29 wt % based on the weight of theparticle. The particle may comprise no greater than 50 wt % or even lessthan 40 wt % zeolite (anhydrous basis). The alkali metal aluminosilicatemay be either crystalline or amorphous or mixtures thereof, having thegeneral formula: 0.8-1.5 Na₂O. A₂O₃. 0.8-6 SiO₂. These materials containsome bound water.

Suitable zeolites are described for example, in GB 1 473 201 (Henkel)and GB 1 429 143 (Procter & Gamble). The preferred sodiumaluminosilicates of this type are the well-known commercially availablezeolites A, X and P, and mixtures thereof. The zeolite may be the thecommercially available zeolite 4A now widely used in laundry detergentpowders. The zeolite builder incorporated in the compositions of theinvention may be maximum aluminium zeolite P (zeolite MAP) as describedand claimed in EP 384 070B (Unilever). Zeolite MAP is defined as analkali metal aluminosilicate of the zeolite P type having a silicon toaluminium ratio not exceeding 1.33, preferably not exceeding 1.15.

The weight ratio of the zeolite to the polycarboxylate polymer in theslurry for spray-drying is from 4:1 to 1:2, preferably from 3:1 to 1:1and most preferably from 3:1 to 1.5:1. Particles having such a weightratio have been found to provide a cleaning benefit when used incombination with other cleaning components in a fully formulated laundrydetergent.

In a further advantageous embodiment of the invention, preferably thespray dried particle also comprises from 0.05 to 50 wt %, or 0.5 to 18wt % or even 2 to 15 wt % of a shear thinning component. At higherlevels, the viscosity is too low for effective spray-drying processes.This may be any shear-thinning detergent additive. It may be ahydrotrope or wax but is preferably a soap. Any conventional soap may beused. The shear-thinning component It is preferably added to the spraydrying process by incorporation of solid particles which may be flakesor noodles or other solid particles of soap into the slurry forspray-drying. Alternatively, where the slurry is sufficiently alkalineto form the soap salt in situ, a fatty acid may be added to the slurryto generate soap in situ. The inventors have found an additionalsurprising benefit associated with the use of shear-thinning componentscomprising soap; soap is often associated with a problem of residues onlaundered clothes particularly noticeable on dark-coloured fabrics. Theinventors have found that incorporation of the soap into the particlesof the present invention produces a significant benefit in reducingthese residues.

In a further embodiment of the invention, surfactant is present in theslurry for spray-drying. Surfactants may be added directly to the slurryfor spray-drying or the acid precursors of the anionic surfactants maybe used so that the surfactant is formed in situ, as described above forin situ soap formation. Any desired level of surfactant may be present,but where present surfactant is generally added into the slurry forspray-drying in an amount to result in an amount of surfactant in thefinished particle of from 1 to 50 wt %, or from 2 to 35 or 15 or even to10 wt % based on the weight of the finished particle.

Suitable surfactants may be any used in detergent compositions asdescribed below. Preferred are the anionic surfactants described below,particularly alkyl benzene sulphonate surfactants.

In addition it has been found to be highly advantageous for processingof the slurry and for producing well-structured particles to incorporateinto the slurry for spray-drying a viscosity modifier.

In addition, a highly preferred component for addition to the slurry isa cationic amine component, particularly for example alkoxylatedcationic diamines, polyamines or polymers of mixtures thereof,particularly as described in EP-A-111965. It has been found that suchcomponents not only provide a clay soil removal/anti-redepositionbenefit in the final cleaning composition but also help in theprocessing of the slurry and in providing well-structured particles.Particularly preferred cationic amine components are optionallysulphated or sulphonated and selected from the group consisting of:

-   1) ethoxylated cationic monoamines having the formula:-   2) ethoxylated cationic diamines having the formula:    wherein M¹ is an N+ or N group; each M² is an N+ or N group, and at    least one M² is an N+group;-   3) ethoxylated cationic polyamines having the formula:-   4) mixtures thereof;    wherein A¹ is    -   R is H or C₁-C₄ alkyl or hydroxyalkyl, R¹ is C₂-C₁₂ alkylene,        hydroxyalkylene, alkenylene, arylene or alkarylene, or a C₂-C₃        oxyalkylene moiety having from 2 to about 20 oxyalkylene units        provided that no O—N bonds are formed; each R² is C₁-C₄ alkyl or        hydroxyalkyl, the moiety —L-X, or two R² together form the        moiety —(CH₂)_(r)—A²—(CH₂)_(s)—, wherein A² is —O— or —CH₂—, r        is 1 or 2, s is 1 or 2 and r+s is 3 or 4; each R³ is C₁-C₈ alkyl        or hydroxyalkyl, benzyl, the moiety L-X, or two R³ or one R² and        one R³ together form the moiety —(CH₂)_(r)—A²—(CH₂)_(s)—; R⁴ is        a substituted C₃-C₁₂ alkyl, hydroxyalkyl, alkenyl, aryl or        alkaryl group having p substitution sites; R⁵ is C₁-C₁₂ alkenyl,        hydroxyalkylene, alkenylene, arylene or alkarylene, or a C₂-C₃        oxyalkylene moiety having from 2 to about 20 oxyalkylene units        provided that no O—O or O—N bonds are formed; X is a nonionic        group selected from the group consisting of H, C₁-C₄ alkyl or        hydroxyalkyl ester or ether groups, and mixtures thereof, L is a        hydrophilic chain which contains the polyoxyalkylene moiety        —[(R⁶O)_(m)(CH₂CH₂O)_(n)]—;    -   wherein R⁶ is C₃-C₄ alkylene or hydroxyalkylene and m and n are        numbers such that the moiety —(CH₂CH₂O)_(n)— comprises at least        about 50% by weight of said polyoxyalkylene moiety; d is 1 when        M² is N+ and is 0 when M² is N; n is at least about 16 for said        cationic monoamines, is at least about 6 for said cationic        diamines and is at least about 3 for said cationic polyamines; p        is from 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is 1        when q is 1. Diamines are preferred, especially diamines        represented by the formula:        bis((C₂H₅O)(C₂H₄O)_(n))(CH₃)—N⁺—C_(x)H_(2x)—N⁺—(CH₃)-bis((C₂H₄O)_(n)(C₂H₅O)),        wherein, n=from 10 to 50 and x=from 1 to 20.

In a further embodiment of the invention, chelants or mixtures ofchelants are present in the particles of the invention, generally atlevels from 0 to 45 wt %, preferably at levels from 1 to 20 wt % or even2 to 15 wt %. Suitable chelants can be selected from the groupconsisting of carboxylates, phosphonates, polyfunctionally-substitutedaromatic chelants and mixtures thereof. The chelant is preferably aphosphonic acid or succinic acid, or salt thereof.

Useful carboxylates include ethylenediaminetetracetates (“EDTA”),N-hydroxyethylethylene diaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylene tetraaminehexacetates,diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal,ammonium, and substituted ammonium salts thereof, and mixtures thereof.

Useful phosphonates include ethylenediaminetetrakis(methylenephosponates), sold as DEQUEST®. Preferably these aminophosphonates do not contain alkyl or alkenyl groups with more than about6 carbon atoms. Particularly preferred chelants are diethylene triaminepenta (methylene phosphonic acid) (“DTPMP”) and ethylene diamine tetra(methylene phosphonic acid) (EDTMP) and hydroxyethylenediphosphonate(HEDP).

Polyfunctionally-substituted aromatic chelants are also useful in thecomponents herein. See U.S. Pat. No. 3,812,044, issued May 21, 1974, toConnor et al. Preferred compounds of this type in acid form aredihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelant for use herein is ethylenediamine-N,N-disuccinate (“EDDS”), especially the [S,S] isomer asdescribed in U.S. Pat. No. 4,704,233, issued on Nov. 3, 1987, to Hartmanand Perkins.

Magnesium salts, particularly magnesium sulphate, have been found to beuseful in ensuring efficient processing in the spray drying process. Inparticular when chelant is present in the particles of the invention,preferably a magnesium salt is also present. Generally the magnesiumsalt will be present at levels of from 040 wt % of the particle,preferably 0.1 to 10 wt %, more preferably from 0.5 to 5 wt %. Magnesiumsulphate is particularly preferred. The chelating agent may bepre-complexed with a metal salt such as magnesium in order to providesome protection from degradation in the presence of bleach. Preferablythis is done by dissolving a salt of the metal ion into a solution ofthe chelating agent in the required ratios. The molar ratio of metal ionto chelating agent is preferably at least 1:1, the present inventionallows molar ratios of greater than 3:1 to be prepared, most preferredis a molar ratio of about 5:1. Again, whilst any metal salt may be used,magnesium sulphate is most preferred.

The particles of the present invention generally also contain anadditional inorganic component such as sodium carbonate, phosphate orsilicate. Sodium carbonate and/or silicate are preferred, sodiumcarbonate being most preferred. Such an inorganic component ispreferably added in amounts from 0 up to 30 wt %, generally in amountsfrom 1 to 20 wt % or from 2 to 15 wt %.

In a further embodiment of the invention, the particles additionallycontain other ingredients which are incorporated in detergentcompositions in minor amounts, such as at levels below 10 wt %, moreusually below 5 wt %, or even below 2 wt % or even lower in the finisheddetergent product. Examples of such materials include polymers useful indetergent compositions such as soil release polymers, opticalbrighteners, dye-transfer inhibitors (such as PVP, PVNO, PVPVI andcombinations thereof), anti-redeposition agents such as CMC, etc. Inparticular the present invention is useful for incorporating into adetergent composition components which are used at low levels infinished product and which are available from suppliers in anaqueous-based form such as a solution of suspension or dispersion inwater. These materials can be added directly to the slurry forspray-drying.

The particles of the present invention are made by a spray-dryingprocess. The polymer, zeolite and optional additional ingredients aremixed with water to form a slurry which is then spray-dried byconventional means (usually using warm air drying although spray coolingmay also be useful). Generally this will be in a spray-drying towerusing a high pressure (e.g. 6000-700 kPa) spray nozzle. Spinning discatomisers may also be used. Generally raw materials which are providedby suppliers in solution or dispersion in water are pre-mixed and thesolids including zeolite subsequently added.

The particles produced will generally have a bulk density at least 300g/l or at least 400 g/l and up to 1000 g/l or 900 g/l or below (asmeasured by the method now described). The final density of theparticles and compositions herein can be measured by a simple techniquewhich involves dispensing a quantity of the granular material into acontainer of known volume, measuring the weight of material andreporting the density as grams/liter. The method used herein allows thematerial to flow into the measuring container under gravity, and withoutpressure or other compaction in the measuring container. The densitymeasurements should be run at room temperature. The granular materialwhose density is being measured should be at least 24 hours old andshould be held at room temperature for 24 hours prior to testing. Arelative humidity of 50% or less is convenient. Of course, any clumps inthe material should be gently broken up prior to running the test. Thesample of material is allowed to flow through a funnel mounted on afilling hopper and stand (#150; Seedburo Equipment Company, Chicago,Ill.) into an Ohaus cup of known volume and weight (# 104; Seedburo).The top of the cup is positioned about 50 mm from the bottom of thefunnel, and the cup is filled to overflowing. A spatula or otherstraight edge is then scraped over the top of the cup, without vibrationor tapping, to level the material, thereby exactly and entirely fillingthe cup. The weight of material in the cup is then measured. Density canbe reported as g/l. Two repeat runs are made and the bulk density isreported as an average of the three measurements. Relative error isabout 0.4%.

In a further embodiment of the invention the particles are furtherprocessed to incorporate them into conventional granules such asagglomerates or extrudates. In this embodiment of the invention, anysolid particulate in a conventional granulation process is wholly orpartially replaced by the spray-dried particles of the presentinvention. Suitable conventional and known granulation processes includeusing a pan-granulator, fluidized bed, Schugi mixer, Lodige ploughsharemixer, rotating drum or other low energy mixers, marumeriser orspheroniser; by compaction, including extrusion optionally withspheronising or marumerising, and tabletting; when melt binding agentsare used by prilling and pastilling using a Sandvik Roto Former; and byhigh shear processes in which the mixers have a high speed stirring andcutting action. Suitable mixers will be well known to those skilled inthe art.

Suitable processes are described in the patent literature: an example ofan agglomeration process is described in U.S. Pat. No. 5,133,924(Appel). An example of a suitable fluidised bed agglomeration process isdescribed for example in WO97/22685 (Dhanuka). Suitable extrusionprocesses are described for example in WO97/03181 (EP-A-840780) (Henkel)or in EP-A-518888 (Henkel).

Detergent Compositions Incorporating the Particles.

In accordance with a further embodiment of the invention, there isprovided a detergent composition comprising a particle as describedabove. Suitable detergent compositions may be for any cleaning purpose,but the invention is particularly directed to laundry washingapplications. The detergent composition will generally be in the form ofa solid composition. Solid compositions include powders, granules,noodles, flakes, bars, tablets, and combinations thereof. The detergentcomposition may be in the form of a liquid composition. The detergentcomposition may also be in the form of a paste, gel, liqui-gel,suspension, or any combination thereof. The detergent composition may beat least partially enclosed, preferably completely enclosed, by a filmor laminate such as a water-soluble and/or water-dispersible material.Preferred water-soluble and/or water-dispersible materials are polyvinylalcohols and/or carboxymethyl celluloses.

The detergent compositions of the invention are preferably granulardetergents having an overall bulk density of from 350 to 1000 g/l, morepreferably 550 to 1000 g/l or even 600 to 900 g/l. Generally theparticles of the invention will be mixed with other detergent particlesincluding combinations of agglomerates, spray-dried powders and/or dryadded materials such as bleaching agents, enzymes etc, to provide alevel of polycarboxylate polymer in the finished product from 0.1 orfrom 1 wt % based on finished product up to 10 wt %, or up to 7 wt % oreven up to 5 wt %. Generally this means that the particles of theinvention may be added into a detergent composition in amounts generallyfrom 1 to 30 wt % based on finished product, or from 1 to 20 wt % orfrom 1 to 10 wt % based on finished product.

Preferably, the detergent particles or the composition has a sizeaverage particle size of from 200 μm to 2000 μm, preferably from 350 μmto 600 μm.

As described above, detergent compositions comprising the particles madeby the process of the invention will comprise at least some of the usualdetergent adjunct materials, such as agglomerates, extrudates, otherspray dried particles having different composition to those of theinvention, or dry added materials. Conventionally, surfactants areincorporated into agglomerates, extrudates or spray dried particlesalong with solid materials, usually builders, and these may be admixedwith the spray dried particles of the invention. However, as describedabove some or all of the solid material may be replaced with theparticles made according to the invention.

The detergent adjunct materials are typically selected from the groupconsisting of detersive surfactants, builders, polymeric co-builders,bleach, chelants, enzymes, anti-redeposition polymers, soil-releasepolymers, polymeric soil-ispersing and/or soil-suspending agents,dye-transfer inhibitors, fabric-integrity agents, suds suppressors,fabric-softeners, flocculants, perfumes, whitening agents, photobleachand combinations thereof.

The precise nature of these additional components, and levels ofincorporation thereof will depend on the physical form of thecomposition or component, and the precise nature of the washingoperation for which it is to be used.

A highly preferred adjunct component is a surfactant. Preferably, thedetergent composition comprises one or more surfactants. Typically, thedetergent composition comprises (by weight of the composition) from 0%to 50%, preferably from 5% and more preferably from 10 or even 15 wt %to 40%, or to 30%, or to 20% one or more surfactants. Preferredsurfactants are anionic surfactants, non-ionic surfactants, cationicsurfactants, zwitterionic surfactants, amphoteric surfactants, cationicsurfactants and mixtures thereof.

Preferred anionic surfactants comprise one or more moieties selectedfrom the group consisting of carbonate, phosphate, sulphate, sulphonateand mixtures thereof. Preferred anionic surfactants are C₈₋₁₈ alkylsulphates and C₈₋₁₈ alkyl sulphonates. Suitable anionic surfactantsincorporated alone or in mixtures in the compositions of the inventionare also the C₈₋₁₈ alkyl sulphates and/or C₈₋₁₈ alkyl sulphonatesoptionally condensed with from 1 to 9 moles of C₁₋₄ alkylene oxide permole of C₈₋₁₈ alkyl sulphate and/or C₈₋₁₈ alkyl sulphonate. The alkylchain of the C₈₋₁₈ alkyl sulphates and/or C₈₋₁₈ alkyl sulphonates may belinear or branched, preferred branched alkyl chains comprise one or morebranched moieties that are C₁₋₆ alkyl groups. Other preferred anionicsurfactants are C₈₋₁₈ alkyl benzene sulphates and/or C₈₋₁₈ alkyl benzenesulphonates. The alkyl chain of the C₈₋₁₈ alkyl benzene sulphates and/orC₈₋₁₈ alkyl benzene sulphonates may be linear or branched, preferredbranched alkyl chains comprise one or more branched moieties that areC₁₋₆ alkyl groups.

Other preferred anionic surfactants are selected from the groupconsisting of: C₈₋₁₈ alkenyl sulphates, C₈₋₁₈ alkenyl sulphonates, C₈₋₁₈alkenyl benzene sulphates, C₈₋₁₈ alkenyl benzene sulphonates, C₈₋₁₈alkyl di-methyl benzene sulphate, C₈C₈ alkyl di-methyl benzenesulphonate, fatty acid ester sulphonates, di-alkyl sulphosuccinates, andcombinations thereof. The anionic surfactants may be present in the saltform. For example, the anionic surfactant may be an alkali metal salt ofone or more of the compounds selected from the group consisting of:C₈₋₁₈ alkyl sulphate, C₈₋₁₈ alkyl sulphonate, C₈₋₁₈ alkyl benzenesulphate, C₈-C₁₈ alkyl benzene sulphonate, and combinations thereof.Preferred alkali metals are sodium, potassium and mixtures thereof.Typically, the detergent composition comprises from 10% to 30 wt %anionic surfactant.

Preferred non-ionic surfactants are selected from the group consistingof: C₈₋₁₈ alcohols condensed with from 1 to 9 of C₁-C₄ alkylene oxideper mole of C₈₋₁₈ alcohol, C₈₋₁₈ alkyl N—C₁₋₄ alkyl glucamides, C₈₋₁₈amido C₁₋₄ dimethyl amines, C₈₋₁₈ alkyl polyglycosides, glycerolmonoethers, polyhydroxyamides, and combinations thereof. Typically thedetergent compositions of the invention comprises from 0 to 15,preferably from 2 to 10 wt % non-ionic surfactant.

Preferred cationic surfactants are quaternary ammonium compounds.Preferred quaternary ammonium compounds comprise a mixture of long andshort hydrocarbon chains, typically alkyl and/or hydroxyalkyl and/oralkoxylated alkyl chains. Typically, long hydrocarbon chains are C₈₋₁₈alkyl chains and/or C₈₋₁₈ hydroxyalkyl chains and/or C₁₋₁₈ alkoxylatedalkyl chains. Typically, short hydrocarbon chains are C₁₋₄ alky chainsand/or C₁₋₄ hydroxyalkyl chains and/or C₁₋₄ alkoxylated alkyl chains.Typically, the detergent composition comprises (by weight of thecomposition) from 0% to 20% cationic surfactant.

Preferred zwitterionic surfactants comprise one or more quaternizednitrogen atoms and one or more moieties selected from the groupconsisting of: carbonate, phosphate, sulphate, sulphonate, andcombinations thereof. Preferred zwitterionic surfactants are alkylbetaines. Other preferred zwitterionic surfactants are alkyl amineoxides. Catanionic surfactants which are complexes comprising a cationicsurfactant and an anionic surfactant may also be included. Typically,the molar ratio of the cationic surfactant to anionic surfactant in thecomplex is greater than 1:1, so that the complex has a net positivecharge.

A further preferred adjunct component is a builder. Preferably, thedetergent composition comprises (by weight of the composition and on ananhydrous basis) from 5% to 50% builder. Preferred builders are selectedfrom the group consisting of: inorganic phosphates and salts thereof,preferably orthophosphate, pyrophosphate, tri-poly-phosphate, alkalimetal salts thereof, and combinations thereof, polycarboxylic acids andsalts thereof, preferably citric acid, alkali metal salts of thereof,and combinations thereof; aluminosilicates, salts thereof, andcombinations thereof, preferably amorphous aluminosilicates, crystallinealuminosilicates, mixed amorphous/crystalline aluminosilicates, alkalimetal salts thereof, and combinations thereof, most preferably zeoliteA, zeolite P, zeolite MAP, salts thereof, and combinations thereof,silicates such as layered silicates, salts thereof, and combinationsthereof, preferably sodium layered silicate; and combinations thereof.

A preferred adjunct component is a bleaching agent. Preferably, thedetergent composition comprises one or more bleaching agents. Typically,the composition comprises (by weight of the composition) from 1% to 50%of one or more bleaching agent. Preferred bleaching agents are selectedfrom the group consisting of sources of peroxide, sources of peracid,bleach boosters, bleach catalysts, photo-bleaches, and combinationsthereof. Preferred sources of peroxide are selected from the groupconsisting of: perborate monohydrate, perborate tetra-hydrate,percarbonate, salts thereof, and combinations thereof. Preferred sourcesof peracid are selected from the group consisting of: bleach activatortypically with a peroxide source such as perborate or percarbonate,preformed peracids, and combinations thereof. Preferred bleachactivators are selected from the group consisting of:oxy-benzene-sulphonate bleach activators, lactam bleach activators,imide bleach activators, and combinations thereof. A preferred source ofperacid is tetra-acetyl ethylene diamine (TAED)and peroxide source suchas percarbonate. Preferred oxy-benzene-sulphonate bleach activators areselected from the group consisting of: nonanoyl-oxy-benzene-sulponate,6-nonamido-caproyl-oxy-benzene-sulphonate, salts thereof, andcombinations thereof. Preferred lactam bleach activators areacyl-caprolactams and/or acyl-valerolactams. A preferred imide bleachactivator is N-nonanoyl-N-methyl-acetamide.

Preferred preformed peracids are selected from the group consisting ofN,N-pthaloyl-amino-peroxycaproic acid, nonyl-amido-peroxyadipic acid,salts thereof, and combinations thereof. Preferably, the STW-compositioncomprises one or more sources of peroxide and one or more sources ofperacid. Preferred bleach catalysts comprise one or more transitionmetal ions. Other preferred bleaching agents are di-acyl peroxides.Preferred bleach boosters are selected from the group consisting of:zwitterionic imines, anionic imine polyions, quaternary oxaziridiniumsalts, and combinations thereof. Highly preferred bleach boosters areselected from the group consisting of: aryliminium zwitterions,aryliminium polyions, and combinations thereof. Suitable bleach boostersare described in U.S. 360568, U.S. 5360569 and U.S. 5370826.

A preferred adjunct component is an anti-redeposition agent. Preferably,the detergent composition comprises one or more anti-redepositionagents. Preferred anti-redeposition agents are cellulosic polymericcomponents, most preferably carboxymethyl celluloses.

A preferred adjunct component is a chelant. Preferably, the detergentcomposition comprises one or more chelants. Preferably, the detergentcomposition comprises (by weight of the composition) from 0.01% to 10%chelant. Preferred chelants are selected from the group consisting of:hydroxyethane-dimethylene-phosphonic acid, ethylene diaminetetra(methylene phosphonic) acid, diethylene triamine pentacetate,ethylene diamine tetraacetate, diethylene triamine penta(methylphosphonic) acid, ethylene diamine disuccinic acid, and combinationsthereof.

A preferred adjunct component is a dye transfer inhibitor. Preferably,the detergent composition comprises one or more dye transfer inhibitors.Typically, dye transfer inhibitors are polymeric components that trapdye molecules and retain the dye molecules by suspending them in thewash liquor. Preferred dye transfer inhibitors are selected from thegroup consisting of: polyvinylpyrrolidones, polyvinylpyridine N-oxides,polyvinylpyrrolidone-polyvinylimidazole copolymers, and combinationsthereof.

A preferred adjunct component is an enzyme. Preferably, the detergentcomposition comprises one or more enzymes. Preferred enzymes areselected from then group consisting of: amylases, arabinosidases,carbohydrases, cellulases, chondroitinases, cutinases, dextranases,esterases, β-glucanases, gluco-amylases, hyaluronidases, keratanases,laccases, ligninases, lipases, lipoxygenases, malanases, mannanases,oxidases, pectinases, pentosanases, peroxidases, phenoloxidases,phospholipases, proteases, pullulanases, reductases, tannases,transferases, xylanases, xyloglucanases, and combinations thereof.Preferred enzymes are selected from the group consisting of: amylases,carbohydrases, cellulases, lipases, proteases, and combinations thereof.

A preferred adjunct component is a fabric integrity agent. Preferably,the detergent composition comprises one or more fabric integrity agents.Typically, fabric integrity agents are polymeric components that depositon the fabric surface and prevent fabric damage during the launderingprocess. Preferred fabric integrity agents are hydrophobically modifiedcelluloses. These hydrophobically modified celluloses reduce fabricabrasion, enhance fibre-fibre interactions and reduce dye loss from thefabric. A preferred hydrophobically modified cellulose is described inWO99/14245. Other preferred fabric integrity agents are polymericcomponents and/or oligomeric components that are obtainable, preferablyobtained, by a process comprising the step of condensing imidazole andepichlorhydrin.

A preferred adjunct component is a salt. Preferably, the detergentcomposition comprises one or more salts. The salts can act as alkalinityagents, buffers, builders, co-builders, encrustation inhibitors,fillers, pH regulators, stability agents, and combinations thereof.Typically, the detergent composition comprises (by weight of thecomposition) from 5% to 60% salt. Preferred salts are alkali metal saltsof aluminate, carbonate, chloride, bicarbonate, nitrate, phosphate,silicate, sulphate, and combinations thereof. Other preferred salts arealkaline earth metal salts of aluminate, carbonate, chloride,bicarbonate, nitrate, phosphate, silicate, sulphate, and combinationsthereof. Especially preferred salts are sodium sulphate, sodiumcarbonate, sodium bicarbonate, sodium silicate, sodium sulphate, andcombinations thereof. Optionally, the alkali metal salts and/or alkalineearth metal salts may be anhydrous.

A preferred adjunct component is a soil release agent. Preferably, thedetergent composition comprises one or more soil release agents.Typically, soil release agents are polymeric compounds that modify thefabric surface and prevent the redeposition of soil on the fabric.Preferred soil release agents are copolymers, preferably blockcopolymers, comprising one or more terephthalate unit. Preferred soilrelease agents are copolymers that are synthesised fromdimethylterephthalate, 1,2-propyl glycol and methyl cappedpolyethyleneglycol. Other preferred soil release agents are anionicallyend capped polyesters.

A preferred adjunct component is a soil suspension agent. Preferably,the detergent composition comprises one or more soil suspension agents.Preferred soil suspension agents are polymeric polycarboxylates.Especially preferred are polymers derived from acrylic acid, polymersderived from maleic acid, and co-polymers derived from maleic acid andacrylic acid. In addition to their soil suspension properties, polymericpolycarboxylates are also useful co-builders for laundry detergents.Other preferred soil suspension agents are alkoxylated polyalkyleneimines. Especially preferred alkoxylated polyalkylene imines areethoxylated polyethylene imines, or ethoxylated-propoxylatedpolyethylene imine. Other preferred soil suspension agents arerepresented by the formula:bis((C₂H₅O)(C₂H₄O)_(n))(CH3)—N⁺—C_(x)H_(2x)—N⁺—(CH₃)-bis((C₂H₄O)_(n)(C₂H₅O)),wherein, n=from 10 to 50 and x=from 1 to 20. Optionally, the soilsuspension agents represented by the above formula can be sulphatedand/or sulphonated.Softening System

The detergent compositions of the invention may comprise softeningagents for softening through the wash such as clay optionally also withflocculant and enzymes.

Further more specific description of suitable detergent components canbe found in WO97/111151.

EXAMPLES

The following are examples of the invention.

Example A

TABLE 1 % slurry Raw Material Example 1 Example 2 EDDS (ethylenediamine-2.8 N,N′-disuccinic acid (S,S isomer) in the form of its sodium salt)MgSO4 1.1 — Na₂SO₄ — 0.7 Maleic acid/acrylic acid 10.8 13.0 copolymer(salt form) Sokalan CP5 (tradename from BASF) HEDP (1,1- 5.6 3.1hydroxyethane diphosphonic acid) C₁₂₋₁₈ alkyl benzene — 3.1 sulphonate(Na salt) LAS Soap 6.5 — Zeolite (anhydrous 37.0 30.4 basis)Hexamethylene — 2.5 diaminetetra (ethoxylate₂₄) diquat with MeClMiscellaneous 5.6 7.2 Water 30.6 40.0 Total parts 100.0 100.0

homogeneous aqueous slurry of the components shown above was made upwith the moisture content shown. The slurry was heated to 80° C. and fedunder high pressure, (6,000-7,000 kPa), into a conventionalcounter-current spray drying tower with an air inlet temperature of300-310° C. The atomised slurry was dried to produce a granular solidwhich was then cooled and sieved to remove oversize (>2 mm). Fine (<0.15mm) material was elutriated with the exhaust air in the spray-dryingtower and collected in a containment system. The finished granules had amoisture content of about 10% by weight, a bulk density of 383 g/l and aparticle size distribution such that 56.4% by weight of the granuleswere between 150-710 microns in size. The particles formed werefree-flowing. The spray-dried powder had a composition as shown in table2 below. TABLE 2 % Spray dried granule Raw Material Example 1 Example 2EDDS 3.7 — MgSO4 1.5 — Na₂SO₄ — 1.1 MA/AA (Sokalan CP5) 14.0 21.0 HEDP7.3 5.0 LAS — 5.0 Soap 8.4 — Zeolite A 47.9 49.0 Diamine — 4.0Miscellaneous 7.4 4.9 Water 9.8 10.0 Total Parts 100 100

These particles of example A (A(1) or A(2)) are incorporated into thefollowing solid laundry detergent compositions according to theinvention (Table 3). Amounts given below are percentages by weight ofthe fully formulated detergent composition. TABLE 3 Ingredient A B C D EExample A particles   7%  13% 15%  10%  10% Sodium linear C₁₁₋₁₃  11% 12% 10%  18%  15% alkylbenzene sulfonate R₂N⁺(CH₃)₂(C₂H₄OH), 0.6%   1%0.6% wherein R₂ = C₁₂₋₁₄ alkyl group Sodium C₁₂₋₁₈ linear alkyl 0.3%  2%  2% sulfate condensed with an average of 3 to 5 moles of ethylene oxideper mole of alkyl sulfate Mid chain methyl branched 1.4% 1.2%  1% sodiumC₁₂₋C₁₄ linear alkyl sulfate Sodium C₁₂₋₁₈ linear alkyl 0.7% 0.5%sulfate C₁₂₋₁₈ linear alkyl ethoxylate   3%  2% condensed with anaverage of 3-9 moles of ethylene oxide per mole of alkyl alcohol Citricacid   2% 1.5%   2% Sodium tripolyphosphate 20%  25%  22% (anhydrousweight given) Sodium carboxymethyl 0.2% 0.2% 0.3% cellulose Sodiumpolyacrylate 0.5%  1% 0.7% polymer having a weight average molecularweight of from 3000 to 5000 Copolymer of 1.2% 0.5% maleic/acrylic acid,having a weight average molecular weight of from 50,000 to 90,000,wherein the ratio of maleic to acrylic acid is from 1:3 to 1:4 (SokalanCP5 from BASF) Diethylene triamine 0.2% 0.5%  0.2% 0.3% pentaacetic acidProteolytic enzyme having 0.2% 0.2% 0.5%  0.4% 0.3% an enzyme activityof from 15 mg/g to 70 mg/g Amyolitic enzyme having 0.2% 0.2% 0.3%  0.4%0.3% an enzyme activity of from 25 mg/g to 50 mg/g Lipolytic enzymehaving an 0.2% 0.1%  enzyme activity of 5 mg/g to 25 mg/g Anhydroussodium 20%   5%   8% perborate monohydrate Sodium percarbonate  10%  12%Magnesium sulfate Nonanoyl oxybenzene   2% 1.2% sulfonateTetraacetylethylenediamine   3%   4%  2% 0.6% 0.8% Brightener 0.1% 0.1%0.2%  0.1% 0.1% Sodium carbonate  10%  10% 10%  19%  22% Sodium sulfate 20%  15%  5%  13%   1% Zeolite A  20%  15%   2%  14% Sodium silicate(2.0 R)  0.2%   1%   1% Crystalline layered silicate   3%   5% 10%Photobleach 0.002%  Polyethylene oxide having a   2%   1% weight averagemolecular weight from 100 to 10,000 Perfume spray-on 0.2% 0.5% 0.25%  0.1% Starch encapsulated 0.4% perfume Silicone based suds 0.05%  0.05% 0.02%  suppressor Miscellaneous and moisture To 100% To 100% To 100% To100% To 100%

1. A method for making a laundry detergent particle comprising from (a)10 to 60 wt % (anhydrous basis) zeolite, (b) 12 to 75 wt %polycarboxylate polymer, and (c) optional additional ingredients to 100%by weight, said method comprising preparing an aqueous slurry comprisingzeolite, and polycarboxylate polymer and optional additional ingredientsand spray-drying the slurry, the weight ratio of zeolite (anhydrousbasis) to polycarboxylate polymer in the slurry is from 4:1 to 1:2.
 2. Amethod according to claim 1 in which the slurry is prepared by addingzeolite to an aqueous solution comprising polycarboxylate polymer.
 3. Amethod according to claim 1 in which the spray-dried particle comprises15 to 50 wt % polycarboxylate polymer (salt form).
 4. A method accordingto claim 1 in which the polycarboxylate polymer has a molecular weightgreater than 10
 000. 5. A method according to claim 1 in which soap isadded into the slurry in an amount to produce a level of soap in thespray-dried particle of 0.05 to 20 wt %.
 6. A method according to claim1 in which the particle produced comprises zeolite (anhydrous basis) inan amount of from 29% by weight to no more than 54% by weight based onthe total weight of the particle.
 7. A method according to claim 1 inwhich the slurry for spray-drying also comprises an alkoxylated cationicdiamine, polyamine or polymer of mixtures thereof, optionally sulphatedor sulphonated.
 8. A method according to claim 1 in which the slurry forspray-drying additionally comprises phosphonate or succinate chelant. 9.A method according to claim 1 in which the slurry for spray-dryingadditionally comprises a magnesium salt in an amount such that thefinished particle will comprise magnesium in an amount equivalent to 0.5to 5% by weight magnesium sulphate.
 10. A detergent compositioncomprising spray-dried particles prepared according to claim 1 andadditional surfactant-containing detergent particles, said additionalparticles comprising from 10 to 60% by weight surfactant.
 11. Adetergent composition according to claim 10 in which thesurfactant-containing detergent particles are spray-dried particles,agglomerates or extrudates.
 12. A detergent composition according toclaim 10 in which the spray-dried particles are incorporated into thedetergent composition as part of an agglomerate or extrudate with otherdetergent adjunct ingredients.
 13. A detergent composition according toclaim 10 additionally comprising a soil suspension agent of the formula:bis((C₂H₅O)(C₂H₄O)_(n))(CH₃)—N⁺—C_(x)H_(2x)—N⁺—(CH₃)-bis((C₂H₄O)_(n)(C₂H₅O)),wherein, n=from 10 to 50 and x=from 1 to 20.